TWI498447B - Metal nitride containing film deposition using combination of amino-metal and halogenated metal precursors - Google Patents

Description

Metal nitride-containing thin film deposition using an amine metal in combination with a metal halide precursor

Cross-reference to related applications

The present application claims the benefit of U.S. Provisional Application No. 61/320,236, filed on Apr. 1, 2010, the entire disclosure of which is incorporated herein by reference.

A method of forming a metal nitride-containing film from a combination of an amine metal precursor and a metal halide precursor, preferably a combination of an amine decane precursor and a chlorodecane precursor, to form a film comprising SiN is disclosed. The sequential reaction of the varying amine metal precursor with the metal halide precursor results in the formation of a metal nitride-containing film having varying stoichiometry. Further, the composition of the metal nitride-containing film can be modified based on the structure of the amine-based metal precursor. The disclosed process can be a thermal process or a plasma process at low temperatures.

Metal nitride-containing films such as tantalum nitride (SiN) films are widely used in semiconductor devices and ultra-large scale integrated (ULSI) circuits. In view of the miniaturization and increasing complexity of electronic devices that are increasingly requiring higher LSI mounting densities, SiN films are required to improve their film quality against current leakage. In addition, an SiCN film is also used as an etch stopper in a dual damascene structure for Cu wiring.

Niobium nitride (SiN) films have been investigated for use as in-line etch stop/pad layers in a wire back end (BEOL) process. Within the floating gate transistor, the inter-gate dielectric layer can comprise, for example, SiO ₂ or SiN. In addition, the carbon-doped SiN layer provides high etch resistance.

When the size of a large scale integration (LSI) is scaled down, the film depth should be thinner, requiring a more precisely controlled process (eg, atomic layer deposition (ALD)). In addition, a reduction in deposition temperature is required. ALD is widely used in many processes (eg, SiO ₂ , SiN, and metal films). See, for example, U.S. Patent No. 7,648,927. However, the deposition rate tends to be lower than chemical vapor deposition (CVD). When the deposition temperature is low, the deposition rate of SiN and the film quality are poor.

Many articles have reported the deposition of high quality SiN and SiCN films by PECVD, PEALD using chlorodecane and reactive NH ₃ and the introduction of amines, CH ₄ or C ₂ H ₄ as carbon sources (see, for example, WO 2009/149167 and US2008/0213479).

There is still a need for a more precisely controlled process for depositing a metal nitride containing film.

Notation and naming

Certain abbreviations, symbols and terms are used throughout the following description and claims: abbreviations "A" refers to angstroms and 1 angstrom = 100 micrometers; abbreviation "PECVD" refers to plasma enhanced chemical vapor deposition; abbreviations "CVD" refers to chemical vapor deposition; the abbreviation "RF" refers to radio frequency, the abbreviation "DR" refers to the deposition rate, and the abbreviation "RI" refers to the refractive index.

The term "alkyl" refers to a saturated functional group that exclusively contains carbon and hydrogen atoms. Further, the term "alkyl" refers to a straight chain, branched chain or cyclic alkyl group. Examples of linear alkyl groups include, without limitation, methyl, ethyl, propyl, butyl, and the like. Examples of branched alkyl groups include, without limitation, a third butyl group. Examples of the cyclic alkyl group include, without limitation, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

As used herein, the abbreviation "Me" refers to methyl; the abbreviation "Et" refers to ethyl; the abbreviation "Pr" refers to propyl; the abbreviation "nPr" refers to a chain propyl; the abbreviation "iPr" refers to a different Propyl; the abbreviation "Bu" refers to butyl (n-butyl); the abbreviation "tBu" refers to the third butyl; the abbreviation "sBu" refers to the second butyl; the abbreviation "iBu" refers to isobutyl; The abbreviation "TMS" refers to trimethylsulfonyl.

Standard abbreviations from elements of the periodic table are used herein. It should be understood that elements may be referred to by such abbreviations (eg, Si refers to hydrazine, C refers to carbon, etc.).

The disclosure is a method of forming a metal nitride-containing film. The metal halide precursor is introduced into an ALD reactor containing at least one substrate. The excess metal halide precursor is then removed from the reactor. An amine metal precursor is introduced into the reactor. The excess amine metal precursor is then removed from the reactor. The reactants can optionally be introduced into the reactor. Excess optional reactants are then removed from the reactor. The metal of the metal halide precursor and the metal of the amine metal precursor may be the same or different.

The disclosure is also a method of forming a metal nitride-containing film. The metal halide precursor is introduced into an ALD reactor containing at least one substrate. The excess metal halide precursor is then removed from the reactor. An amine metal precursor is introduced into the reactor. The excess amine metal precursor is then removed from the reactor. The reactants are introduced into the reactor. The excess reactant is then removed from the reactor. The metal of the metal halide precursor and the metal of the amine metal precursor may be the same or different.

The disclosure is also a method of forming a film containing tantalum nitride. The chlorodecane precursor is introduced into an ALD reactor containing at least one substrate. The excess chlorodecane precursor is then removed from the reactor. The amino decane precursor is introduced into the reactor. The excess aminodecane precursor is then removed from the reactor. The reactants can optionally be introduced into the reactor. Excess optional reactants are then removed from the reactor.

The disclosure is also a method of forming a film containing tantalum nitride. The chlorodecane precursor is introduced into an ALD reactor containing at least one substrate. The excess chlorodecane precursor is then removed from the reactor. The amino decane precursor is introduced into the reactor. The excess aminodecane precursor is then removed from the reactor. The reactants are introduced into the reactor. The excess reactant is then removed from the reactor.

Each of the disclosed methods can further include one or more of the following:

‧ The reactants are selected from the group consisting of N ₂ , NH ₃ , N ₂ H ₄ , NMeH ₂ , NEtH ₂ , NMe ₂ H, NEt ₂ H, NMe ₃ , NEt ₃ , MeHNNH ₂ , Me ₂ NNH ₂ , benzoquinone and mixtures thereof;

‧ The reactant is NH ₃ ;

‧ producing a metal nitride-containing film having a specified stoichiometry by varying the order of the method steps;

‧ The halogenated precursor is a metal chloride precursor;

‧ The metal nitride-containing film is a metal carbonitride film containing one or two metals;

‧ The metal is selected from transition metals, metals or non-metallic elements;

‧ The metal is boron or phosphorus;

‧ The metal nitride-containing film is a film containing tantalum nitride;

‧ The metal halide precursor is a chlorodecane precursor;

‧ The amine metal precursor is an amino decane precursor;

‧ The film containing tantalum nitride is a carbon-doped SiN film;

‧ the chlorodecane precursor has the formula Si _a H _b Cl _c , where b+c=2a+2;

‧ a chlorodecane precursor introduced as a mixture;

‧ Aminodecane precursor having the formula H _4-x Si(NR'R") _x wherein x=1, 2, 3 or 4, R' and R" are independently selected from H or alkyl, and R' and R" may be bonded to form a ring structure;

‧ the aminodecane precursor comprises an aminochlorodecane or an aminoalkyl decane;

‧ Aminochloromethane precursors have the formula Cl _4-x Si(NR'R") _x , where x = 2 or 3, R' and R" are independently selected from H or alkyl, and R' and R" are Bonded to form a ring structure; and

‧ The aminoalkyl decane precursor has the formula R''' _4-x Si(NR'R") _x , wherein x = 1, 2 or 3, and R' and R" are independently selected from H or alkyl, R 'and R' may be bonded to form a ring structure, and the R'' group is an alkyl group having less than 3 carbons.

To further understand the nature and objects of the present invention, reference is made to the following embodiments in conjunction with the drawings.

The disclosure is an ALD process for forming a metal nitride-containing film using alternating supply of an amine metal precursor and a metal halide precursor. The sequential reaction of the amine metal precursor with the metal halide precursor produces a dense metal-rich film. The metal of the metal halide precursor may be the same as or different from the metal of the amine metal precursor.

The disclosure also discloses an ALD process for forming a tantalum nitride-containing film (preferably a hafnium carbonitride film) using alternating supply of an amino decane precursor and a chlorodecane precursor under thermal or low temperature plasma conditions. The sequential reaction of the aminodecane precursor with the chlorodecane precursor produces a dense, ruthenium-rich film at temperatures lower than those of many prior art tantalum nitride film deposition processes. The tantalum carbonitride film may be referred to as a tantalum nitride film doped with carbon. Those skilled in the art will recognize that the amount of carbon in the tantalum nitride film is appropriately named. The amount of carbon in the carbon-doped tantalum nitride film is typically less than the amount of carbon in the tantalum carbonitride film. However, those of ordinary skill in the art will further recognize that determining the exact percentage of carbon in an appropriately named film is not defined and will vary from person to person.

The disclosed method forms a metal nitride-containing film (such as SiN) or a metal carbonitride film (such as SiCN) from an amine metal and a metal halide precursor by ALD. The metal nitride-containing film may be a metal carbonitride film containing one or two metals. For example, the metal carbonitride film can be a SiHfCN film. Alternatively, the SiN film can be doped with carbon.

As will be described in further detail in Examples 2 through 4, a metal nitride-containing film having a specified stoichiometry can be produced by varying the order of the disclosed method steps. In addition, the duration of the disclosed method steps can also be varied to "tune" the resulting film.

The metal halide precursor is introduced into an ALD reactor containing one or more substrates. The metal halide precursor can be introduced into the ALD reactor before or after the amine metal precursor. The conditions within the reactor permit at least a portion of the metal halide precursor to self-adsorb to the substrate. Those of ordinary skill in the art will recognize that substrate properties will define a metal halide precursor that undergoes physical or chemical adsorption in this step. For example, if a metal halide precursor is introduced into the reactor after the amine metal precursor, at least a portion of the metal halide precursor will react/chemically adsorb with a portion of the amine metal precursor deposited in the previous step. . Any unadsorbed or "excess" metal halide precursor is removed from the reactor. The metal halide precursor reacts with the NH ₃ /amine based metal precursor at low temperatures.

The metal halide precursor can be a metal chloride precursor. The metal of the metal halide or metal chloride precursor may be any transition metal, metal or non-metal element as generally defined on the periodic table of elements. Preferred transition metals include, but are not limited to, Hf. Preferred metals include, but are not limited to, Zn. Preferred non-metals include, but are not limited to, B, Si, and P. The metal halide precursor can be used as a mixture of two or more metal halide precursors. Preferably, the metal halide precursor is a chlorodecane precursor. An exemplary chlorodecane precursor has the formula Si _a H _b Cl _c , where b+c=2a+2. Exemplary precursors include chloro Silane Silane hexachlorodisilane _{(HCDS), SiCl 4, SiHCl} 3, Si 2 H 5 Cl and the like and mixtures thereof, such as, SiCl ₄ or with HCDS HCDS and SiHCl _3. Preferably, the metal halide precursor comprises HfCl ₄ or HCDS, and more preferably HCDS.

The amine metal precursor is introduced into the reactor. The conditions within the reactor permit at least a portion of the amine-based metal precursor to self-adsorb to the substrate. The amine metal precursor can be introduced into the ALD reactor before or after the metal halide precursor. Again, those skilled in the art will recognize that substrate properties will define an amine metal precursor that undergoes physical or chemical adsorption in this step. For example, if an amine metal precursor is introduced into the reactor after the metal halide precursor, at least a portion of the amine metal precursor will react/chemically adsorb with a portion of the metal halide precursor deposited in the previous step. . Any unadsorbed or "excess" amine metal precursor is then removed from the reactor. N serving as the only source of the prior art Comparative NH ₃ precursor, metal precursor amine C may serve as both the source and the N source. The alkylamine group of the amine metal precursor acts as a good leaving group and produces good adsorption. The change in the ligand of the amine metal precursor provides the ability to modify the carbon content of the metal nitride containing film.

The metal of the amine metal precursor can be any transition metal, metal or non-metal element as generally defined on the periodic table of elements. Preferred transition metals include, but are not limited to, Hf. Preferred metals include, but are not limited to, Zn. Preferred non-metals include, but are not limited to, B, Si, and P. The amine metal precursor can be used as a mixture of two or more amine metal precursors. The amine metal precursor can be an amino decane precursor. An exemplary aminodecane precursor having the formula H _4-x Si(NR'R") _x wherein x=1, 2, 3 or 4, R' and R" are independently selected from H or alkyl, and R' And R" may be bonded to form a ring structure. Alternatively, the amino decane precursor may be an amine chlorodecane precursor or an aminoalkyl decane precursor. An exemplary amino chlorodecane precursor has the formula Cl _4-x Si(NR'R") _x , wherein x = 2 or 3, and R' and R" are as previously defined. The exemplary aminoalkyl decane precursor has the formula R''' _4-x Si (NR'R ") _x , wherein x = 1, 2 or 3, R' and R" are as previously defined, and the R'' group is an alkyl group having less than 3 carbons. Preferably, the amine metal precursor is double (diethylamino) decane (BDEAS), ginseng (dimethylamino) decane (3DMAS), hydrazine (dimethylamino) decane (4DMAS) or hydrazine (ethylmethylamino) hydrazine, and More preferably 3DMAS and/or 4DMAS.

The metal halide precursor and the amine metal precursor (collectively referred to as "precursors") are each individually introduced into the reactor in vapor form. In this context, "individually" and "each" refer to a predecessor of a given class, such as a "halide metal precursor" which may be comprised of one or more halogenated precursors. In the following paragraphs, it is not individually intended to mean that only one vapor of the metal halide precursor is introduced into the reactor.

The precursors can be individually fed to the evaporator in a liquid state, wherein the precursors each evaporate individually before being introduced into the reactor. Each of the precursors may optionally be combined with one or more solvents prior to evaporation. The solvents may be selected from the group consisting of toluene, ethylbenzene, xylene, 1,3,5-trimethylbenzene, decane, dodecane, octane, hexane, pentane or others. The resulting concentration can vary from about 0.05 M to about 2 M.

Alternatively, the precursor may be individually vaporized by passing a carrier gas into a vessel containing each of the precursors or by bubbling a carrier gas into each of the precursors. Each of the precursors may optionally be mixed with one or more solvents in a container. The carrier gas and individual precursors are then introduced into the reactor as a vapor. The carrier gas can include, but is not limited to, Ar, He, N _2, and mixtures thereof. Any dissolved oxygen present in the precursor solution can also be removed by bubbling the carrier gas.

If necessary, the vessel can be heated to a temperature that permits the precursor to be in the liquid phase and have sufficient vapor pressure. The container can be maintained at a temperature in the range of, for example, 0 °C to 150 °C. Those skilled in the art recognize that the temperature of the vessel can be adjusted in a known manner to control the amount of precursor that is evaporated.

The vapor of each precursor can be introduced into the reactor for a time period of from about 0.01 seconds to about 60 seconds, or from about 5 seconds to about 25 seconds, or from about 10 seconds to about 20 seconds.

In one embodiment, the reactants can be introduced into a reactor where the reactants react with the self-adsorbing layer on the substrate. Any unreacted or "excess" reactants are then removed from the reactor. The reactants can be N ₂ , NH ₃ , N ₂ H ₄ , NMeH ₂ , NEtH ₂ , NMe ₂ H, NEt ₂ H, NMe ₃ , NEt ₃ , MeHNNH ₂ , Me ₂ NNH ₂ , benzoquinone, and mixtures thereof. Preferably, the reactant is NH ₃ . However, as will be described in further detail in the examples that follow, the optional reactant step will depend on the desired stoichiometric ratio of the elements in the resulting metal nitride-containing film.

The reactants can be treated by plasma to decompose the reactants into their free radical form. The plasma can be produced or present within the reactor itself. Alternatively, for example, in a remotely located plasma system, the plasma can generally be at a location remote from the reactor. Those skilled in the art will recognize methods and apparatus suitable for such plasma processing.

For example, the reactants can be introduced into a direct plasma reactor (which produces a plasma in the reactor) to produce a plasma treated reactant in the reactor. Exemplary direct plasma reactor technology includes a Trion produced Titan ^TM PECVD system. The reactants can be introduced and maintained in the reactor prior to the plasma treatment. Alternatively, the plasma treatment can occur simultaneously with the introduction of the reactants. The in-situ plasma is typically a 13.56 MHz RF capacitively coupled plasma produced between the showerhead and the substrate holder. The substrate or showerhead can be a charged electrode depending on whether a positive ion collision occurs. Typical applied power in an in-situ plasma generator is from about 100 W to about 1000 W. For the same power input, the use of in-situ plasma to dissociate the reactants is typically less than the use of a remote plasma source to achieve the disassociation of the reactants, and therefore less effective than the far end plasma system in detaching the reactants. This can be beneficial for depositing a metal nitride-containing film on a substrate that is susceptible to plasma damage.

Alternatively, the plasma treated reactant can be produced outside of the reactor. MKS instrument The i reactive gas generator can be used to treat the reactants prior to delivery to the reactor. In 2.45 GHz, 7kW plasma power and changes from about 3 Torr to about 10 Torr at a pressure of the operation, the reaction was over 96% of NF ₃ decomposition efficiency can be decomposed into three F ^- group. Preferably, the remote plasma can be generated from about 1 kW to about 10 kW, more preferably from about 2.5 kW to about 7.5 kW.

The ALD reactor can be a heated vessel having at least one or more substrates disposed therein. The reactor has an outlet that can be connected to a vacuum pump to allow by-product removal from the reactor, or to allow the pressure within the reactor to be modified or adjusted. Examples of suitable ALD reactors include, without limitation, parallel plate reactors, cold wall reactors, hot wall reactors, single wafer reactors, multi-wafer reactors, direct plasma reactors, or Other types of deposition systems suitable for reacting precursors and forming multiple layers.

In general, the reactor contains one or more substrates on which a metal nitride-containing film will be deposited. For example, the reactor can contain from 1 to 200 tantalum wafers having diameters from 25.4 mm to 450 mm. The substrate can be any suitable substrate for use in semiconductor, photovoltaic, flat panel or LCD-TFT device fabrication. The substrate may contain one or more additional layers of material that may be presented from previous fabrication steps. Examples of additional layers of dielectric layers such as dielectric layers and conductive layers. Within the scope of the present application, all of the substrate and any of the layers deposited on the substrate are collectively included within the term substrate. Examples of suitable substrates include, without limitation, metal substrates, metal nitride substrates, tantalum substrates, vermiculite substrates, tantalum nitride substrates, tantalum oxynitride substrates, tungsten substrates, and combinations thereof. In addition, a substrate containing tungsten or a noble metal such as platinum, palladium, rhodium or gold may be used. Preferably, the substrate is a metal film or a metal nitride film.

The temperature of the reactor can be controlled by controlling the temperature of the substrate holder or controlling the temperature of the reactor wall. Devices for heating substrates are known in the art. The reactor is heated to a temperature sufficient to obtain a desired metal nitride-containing film that grows at a sufficient growth rate and has the desired physical state and composition. Non-limiting exemplary temperature ranges to which the reactor can be heated include from about 200 °C to about 700 °C. When utilizing a plasma deposition process, the deposition temperature can vary from about 200 °C to about 550 °C. Alternatively, the deposition temperature may vary from about 400 ° C to about 600 ° C when the thermal process is performed.

The pressure in the ALD reactor is from about 0.1 Torr (13 Pa) to about 10 Torr (1300 Pa).

In a preferred embodiment, the disclosed process utilizes a chlorodecane precursor (preferably HfCl ₄ or HCDS) and an amino decane precursor (preferably 3DMAS, 4DMAS or hydrazine (ethylmethylamino) hydrazine) to form A film containing SiN or SiCN. The resulting film has a very low (from about 0 to about 5 atomic %) chlorine or oxygen content.

The disclosed method solves the problem of film quality with respect to SiN-containing films by atomic layer deposition at low temperatures and C insertion in SiN-containing films.

The disclosed method provides the following advantages over prior methods: - The insertion of carbon into a SiN film having a tunable combination of an amine decane and chlorodecane is due to: - The ratio of the combinations is changed to a film of a different composition.

Example

The following non-limiting examples are provided to further illustrate specific examples of the invention. However, the embodiments are not intended to be exhaustive or to limit the scope of the invention described herein.

Example 1

A dense SiCN film was deposited using the ALD method and a precursor of trichloromethane (3CS) and dimethyl (dimethylamino) decane (3DMAS). The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 100 sccm continuously flowed. The deposition process consisted of the following steps: 1) supplying a pulse of 3 CS of about 1 sccm to the reaction chamber for 10 seconds, 2) removing the 3CS precursor by 100 sccm for 30 seconds, 3) 3DMAS of about 1 sccm. The pulse was supplied to the reaction chamber for 10 seconds, 4) the 3DMAS precursor was purged by 100 sccm of Ar for 30 seconds. Sequences 1) to 4) are repeated until the deposited layer reaches a suitable layer thickness.

The deposited film exhibited a deposition rate of about 0.6 angstroms/cycle. The refractive index is 2.1 or more.

Example 2a

A dense SiCN film was deposited by the ALD method by a hexachlorodioxane (HCDS) and a dimethyl (dimethylamino) decane (3DMAS) precursor and an ammonia (NH ₃ ) reactant. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of 3 DMAS of about 1 sccm into the reaction chamber for 10 seconds, 2) removing the 3DMAS precursor by 55 sccm of Ar for 30 seconds, 3) about 1 sccm of HCDS. The pulse was introduced into the reaction chamber for 10 seconds, 4) the HCDS precursor was purged by 55 sccm of Arrox for 30 seconds, 5) a pulse of about 50 sccm of NH ₃ was introduced into the reaction chamber for 10 seconds, and 6) The NH ₃ reaction was purged by 55 sccm of Ar for 10 seconds. Sequences 1) to 6) are repeated until the deposited layer reaches a suitable layer thickness.

The deposition rate and refractive index of the deposited film are shown in FIG. The atomic composition percentage of each of ruthenium and nitrogen in the obtained film is more than 40% but less than 45%, and the atomic composition percentage of carbon is about 10%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 0% or more but less than 5%. The wet etch rate of the resulting film etched from the HF solution was 4.24 angstroms per minute.

Example 2b

A dense SiCN film was deposited by the ALD method by the HCDS 3DMAS precursor and the ammonia (NH ₃ ) reactant. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of about 1 sccm of HCDS into the reaction chamber for 10 seconds, 2) removing the HCDS precursor by 55 sccm of Ar for 30 seconds, 3) 3 DMA of about 1 sccm. The pulse is introduced into the reaction chamber for 10 seconds, 4) the 3DMAS precursor is removed by 55 sccm of Arrox for 30 seconds, 5) a pulse of about 50 sccm of NH ₃ is introduced into the reaction chamber for 10 seconds, and 6) The NH ₃ reaction was purged by 55 sccm of Ar for 10 seconds. Sequences 1) to 6) are repeated until the deposited layer reaches a suitable layer thickness.

The deposition rate and refractive index of the deposited film are shown in FIG. The atomic composition percentage of ruthenium in the obtained film is more than 45% but less than 50%, and the atomic composition percentage of nitrogen in the obtained film is more than 30% but less than 35%, and the atomic composition percentage of carbon is more than 15% but less than 20%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 0% or more but less than 5%. The wet etch rate of the resulting film etched from the HF solution was 0.54 Å/min.

Example 2c

A dense SiCN film was deposited by the ALD method by using HCDS and 3DMAS precursors. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of 3 DMAS of about 1 sccm into the reaction chamber for 10 seconds, 2) removing the 3DMAS precursor by 55 sccm of Ar for 30 seconds, 3) about 1 sccm of HCDS. The pulse was introduced into the reaction chamber for 10 seconds, and 4) the HCDS precursor was purged by 55 sccm of Ar for 30 seconds. Sequences 1) to 4) are repeated until the deposited layer reaches a suitable layer thickness.

The deposition rate and refractive index of the deposited film are shown in FIG. The atomic composition percentage of ruthenium in the obtained film is more than 50% but less than 55%, the atomic composition percentage of carbon in the obtained film is more than 30% but less than 35%, and the atomic composition percentage of nitrogen is about 10%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 1% or more but less than 5%. The wet etch rate of the resulting film etched from the HF solution was 0.04 Å/min.

Example 3a

A dense SiCN film was deposited by the ALD method by a hexachlorodioxane (HCDS) and a ruthenium (dimethylamino) decane (4DMAS) precursor and an ammonia (NH ₃ ) reactant. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of 4 DMAS of about 1 sccm into the reaction chamber for 10 seconds, 2) removing the 4 DMAS precursor by 55 sccm of Ar for 30 seconds, 3) about 1 sccm of HCDS. The pulse was introduced into the reaction chamber for 10 seconds, 4) the HCDS precursor was purged by 55 sccm of Arrox for 30 seconds, 5) a pulse of about 50 sccm of NH ₃ was introduced into the reaction chamber for 10 seconds, and 6) The NH ₃ reaction was purged by 55 sccm of Ar for 10 seconds. Sequences 1) to 6) are repeated until the deposited layer reaches a suitable layer thickness.

The deposition rate and refractive index of the deposited film are shown in FIG. The atomic composition percentage of nitrogen in the obtained film was about 45%, the atomic composition percentage of ruthenium in the obtained film was more than 40% but less than 45%, and the atomic composition percentage of carbon was more than 5% but less than 10%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 0% or more but less than 5%. The wet etch rate of the resulting film etched from the HF solution was 5.76 angstroms per minute.

Example 3b

ALD process by using HCDS and ammonia 4DMAS precursor and (NH ₃₎ dense reaction was deposited SiCN film. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of about 1 sccm of HCDS into the reaction chamber for 10 seconds, 2) removing the HCDS precursor by 55 sccm of Ar for 30 seconds, and 3) 4 DMAs of about 1 sccm. The pulse is introduced into the reaction chamber for 10 seconds, 4) the 4DMAS precursor is removed by 55 sccm of Ar for 30 seconds, 5) a pulse of about 50 sccm of NH ₃ is introduced into the reaction chamber for 10 seconds, and 6) The NH ₃ reaction was purged by 55 sccm of Ar for 10 seconds. Sequences 1) to 6) are repeated until the deposited layer reaches a suitable layer thickness.

The deposition rate and refractive index of the deposited film are shown in FIG. The atomic composition percentage of ruthenium in the obtained film is more than 40% but less than 45%, the atomic composition percentage of nitrogen in the obtained film is about 40%, and the atomic composition percentage of carbon is more than 10% but less than 15%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 0% or more but less than 5%. The wet etch rate of the resulting film etched from the HF solution was 4.31 Å/min.

Example 3c

A dense SiCN film was deposited by the ALD method by HCDS and 4DMAS precursors. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of 4 DMAS of about 1 sccm into the reaction chamber for 10 seconds, 2) removing the 4 DMAS precursor by 55 sccm of Ar for 30 seconds, 3) about 1 sccm of HCDS. The pulse was introduced into the reaction chamber for 10 seconds, and 4) the HCDS precursor was purged by 55 sccm of Ar for 30 seconds. Sequences 1) to 4) are repeated until the deposited layer reaches a suitable layer thickness.

The deposition rate and refractive index of the deposited film are shown in FIG. The atomic composition percentage of ruthenium in the obtained film is more than 50% but less than 55%, the atomic composition percentage of carbon in the obtained film is more than 30% but less than 35%, and the atomic composition percentage of nitrogen is about 10%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 1% or more but less than 5%. The obtained film was etched by an HF solution at a wet etching rate of 0.15 Å/min.

Example 4a

A dense SiCN film was deposited by the ALD method by a hexachlorodioxane (HCDS) and a bis(diethylamino) decane (BDEAS) precursor and an ammonia (NH ₃ ) reactant. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of about 1 sccm of BDEAS into the reaction chamber for 10 seconds, 2) removing the BDEAS precursor by 55 sccm of Ar for 30 seconds, 3) about 1 sccm of HCDS. The pulse was introduced into the reaction chamber for 10 seconds, 4) the HCDS precursor was purged by 55 sccm of Arrox for 30 seconds, 5) a pulse of about 50 sccm of NH ₃ was introduced into the reaction chamber for 10 seconds, and 6) The NH ₃ reaction was purged by 55 sccm of Ar for 10 seconds. Sequences 1) to 6) are repeated until the deposited layer reaches a suitable layer thickness.

The deposition rate and refractive index of the deposited film are shown in FIG. The atomic composition percentage of ruthenium in the obtained film is slightly more than about 40%, the atomic composition percentage of nitrogen in the obtained film is slightly less than 40%, and the atomic composition percentage of carbon is slightly more than 15%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 0% or more but less than 5%. The resulting film was etched by HF solution at a wet etch rate of 1.65 angstroms per minute.

Example 4b

A dense SiCN film was deposited by the ALD method by using HCDS and BDEAS precursors and ammonia (NH ₃ ) reactants. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of about 1 sccm of HCDS into the reaction chamber for 10 seconds, 2) removing the HCDS precursor by 55 sccm of Ar for 30 seconds, and 3) BDEAS of about 1 sccm. a pulse is introduced into the reaction chamber for 10 seconds, 4) the BDEAS precursor is purged by 55 sccm of Ar for 30 seconds, 5) a pulse of about 50 sccm of NH ₃ is introduced into the reaction chamber for 10 seconds, and 6) The NH ₃ reaction was purged by 55 sccm of Ar for 10 seconds. Sequences 1) to 6) are repeated until the deposited layer reaches a suitable layer thickness.

The deposition rate and refractive index of the deposited film are shown in FIG. The atomic composition percentage of ruthenium in the obtained film was about 45%, the atomic composition percentage of nitrogen in the obtained film was about 30%, and the atomic composition percentage of carbon was about 20%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 0% or more but less than 5%. The wet etch rate of the resulting film etched from the HF solution was 0.54 Å/min.

Example 4c

A dense SiCN film was deposited by the ALD method by using HCDS and BDEAS precursors. The reaction chamber was controlled at 5 Torr, 550 ° C, and Ar of 55 sccm continuously flowed. The deposition process comprises the steps of: 1) introducing a pulse of about 1 sccm of BDEAS into the reaction chamber for 10 seconds, 2) removing the BDEAS precursor by 55 sccm of Ar for 30 seconds, 3) about 1 sccm of HCDS. The pulse was introduced into the reaction chamber for 10 seconds, and 4) the HCDS precursor was purged by 55 sccm of Ar for 30 seconds. Sequences 1) to 4) are repeated until the deposited layer reaches a suitable layer thickness.

The carbon content of the resulting film is too high to allow measurement of the deposition rate and refractive index by ellipsometry. The atomic composition percentage of ruthenium in the obtained film is more than 55% but less than 60%, the atomic composition percentage of carbon in the obtained film is more than 30% but less than 35%, and the atomic composition percentage of nitrogen is slightly more than 5%. The atomic composition percentage of each of chlorine and oxygen in the obtained film was 0% or more but less than 5%. The obtained film was etched by an HF solution at a wet etching rate of 0.15 Å/min.

Example 5

Applicants are convinced that a dense HfSiCN film will be deposited by HfCl ₄ and 3DMAS precursors using the disclosed ALD method. Applicants are convinced that the disclosed method can be used to modify the stoichiometric ratio in the resulting film.

Example 6

Applicants are convinced that a dense HfSiCN film will be deposited by ruthenium (ethylmethylamino) oxime and HCDS precursor using the disclosed ALD method. Applicants are convinced that the disclosed method can be used to modify the stoichiometric ratio in the resulting film.

It will be appreciated that many additional changes in the details, materials, steps, and arrangements of the components may be made by those skilled in the art in the <RTIgt; It has been described and illustrated to explain the nature of the invention. Therefore, the present invention is not intended to be limited to the specific embodiments shown in the embodiments and/or the accompanying drawings.

1 is a graph showing the deposition rate and refractive index of a SiCN film deposited using ginseng (dimethylamino) decane (3DMAS) and hexachlorodioxane (HCDS) according to the disclosed method;

2 is a graph showing deposition rates and refractive index versus distance for a SiCN film deposited using 3DMAS and HCDS in accordance with an alternative method of the disclosed method;

3 is a graph showing deposition rates and refractive index versus distance for a SiCN film deposited using 3DMAS and HCDS in accordance with a second alternative method of the disclosed method;

4 is a graph showing the deposition rate and refractive index of a SiCN film deposited using yttrium (dimethylamino) decane (4DMAS) and hexachlorodioxane (HCDS) according to the disclosed method;

5 is a graph showing deposition rates and refractive index versus distance for a SiCN film deposited using 4DMAS and HCDS in accordance with an alternative method of the disclosed method;

6 is a graph showing deposition rates and refractive index versus distance for a SiCN film deposited using 4DMAS and HCDS in accordance with a second alternative method of the disclosed method;

7 is a graph showing the deposition rate and refractive index of a SiCN film deposited using bis(diethylamino) decane (BDEAS) and hexachlorodioxane (HCDS) according to the disclosed method versus the distance of the film from the inlet; and

8 is a graph showing deposition rates and refractive index versus distance for a SiCN film deposited using BDEAS and HCDS in accordance with an alternative method of the disclosed method.

Claims (4)

A method of forming a nitride-containing film, the method comprising the steps of: a) controlling an ALD reactor at a temperature ranging from about 200 ° C to about 600 ° C; b) introducing hexachlorodioxane to at least one substrate In the ALD reactor; c) removing excess hexachlorodioxane from the reactor; d) introducing bis(diethylamino) decane into the reactor; e) removing excess bis(diethylamino) The decane is purged from the reactor; f) introducing NH ₃ into the reactor; and g) removing excess NH ₃ from the reactor. The method of claim 1, wherein the order of steps (b) through (g) of the method is varied to produce a SiCN film having a specified stoichiometry. A method of forming a SiCN film, the method comprising the steps of: a) controlling an ALD reactor at a temperature ranging from about 200 ° C to about 600 ° C; b) introducing hexachlorodioxane to the ALD reaction containing at least one substrate ; c) removing excess hexachlorodioxane from the reactor; d) introducing hydrazine (dimethylamino) decane into the reactor; e) removing excess hydrazine (dimethylamino) decane from the reactor is cleared; F) ₃ NH2 was introduced into the reactor which, and g) from the reactor ₃ to remove the excess NH. The method of claim 3, wherein the order of steps (b) through (g) of the method is varied to produce a SiCN film having a specified stoichiometry.